Process for producing vinyl chloride resin composition

ABSTRACT

The invention relates to a process for production of vinyl chloride resin composition, by uniform blending of 95 to 70 parts by weight of vinyl chloride resin, and 5 to 30 parts by weight of a modifying component obtained by graft-polymerizing upon a cross-linked copolymer rubber latex a first and then a second grafting component in a sequential two-stage process.

Tanaka et al.

PROCESS FOR PRODUCING VINYL CHLORIDE RESIN COMPOSITION Inventors: Takashi Tanaka; Haruhiko Yusa;

Susumu Chubachi, all of lwaki, Japan Assignee: Kureha Kagaku Kogyo Kabushiki Kaisha, Japan Filed: July 17, 1974 Appl. No.: 489,836

Related US. Application Data Division of Ser. No. 295,577, Oct. 6, 1972, Pat. No.

US. Cl.... 260/876 R; 260/23.7 H; 260/4l.5 R; 260/45.75; 260/879; 260/880 R Int. Cl C08d 9/10; C08f 15/00; C08f 14/00 [451 May 27, 1975 [58] Field of Search 260/876 R, 879, 880 R [56] References Cited UNITED STATES PATENTS 3,264,373 8/1966 Whitworth et al. 260/876 R 3,513,226 5/1970 Hotta 260/376 R 3,652,483 3/1972 Tanaka et al.... 260/29.7 UP 3,775,514 11/1973 Amagi et 31] 260/876 R Primary ExaminerJohn C. Bleutge Assistant Examiner-Richard B. Turer Attorney, Agent, or Firm-Wenderoth, Lind & Ponack [57] ABSTRACT The invention relates to a process for production of vinyl chloride resin composition, by uniform blending of 95 to 70 parts by weight of vinyl chloride resin, and 5 to 30 parts by weight of a modifying component obtained by graft-polymerizing upon a cross-linked copolymer rubber latex a first and. then a second grafting component in a sequential two stage process.

4 Claims, N0 Drawings PROCESS FOR PRODUCING VINYL CHLORIDE RESIN COMPOSITION This is a division, of application Ser. No. 295.577, filed Oct. 6, 1972 now US. Pat. No. 3,842,144.

This invention relates to a process for producing vinyl chloride resin composition which is excellent in its impact strength, and, at the same time has satisfactory weather-resistance and processability. More particularly, the invention is concerned with a method of producing a modifying component consisting of a multicomponent type resin, and a polymer blend of such modifying component and vinyl chloride resin, the former being obtained by graft-polymerizing a grafting component consisting of styrene and methylmethacrylate and containing therein a cross-linking agent upon a cross-linked copolymer rubber consisting of acrylic acid alkyl ester and butadiene, or the crosslinked copolymer rubber of the abovementioned composition, a part of which has been substituted for methylmethacrylate.

As has been well known, vinyl chloride resin possesses various excellent properties, on account of which it has been widely used in variety of fields. However, it has a fatal disadvantage such that it is fragile on impact.

With a view, therefore, to improving the impact strength of this resin, much research and experimentation has been performed. From such research, a resin obtained by graft-polymerizing styrene and methylmethacrylate upon butadiene type rubber (the socalled MBS resin), or a resin obtained by graft polymerizing styrene and acrylonitrile upon the butadiene type rubber (the so-called ABR resin) has recently attained notable fame and development as an impact modifiers of vinyl chloride resin, as a result of which the general notion that vinyl chloride resin is inherently vulnerable to impact is now declining.

However, even the vinyl resin composition blended with the abovementioned MBS or ABS resin is still poor in its weather resistance, and is not durable under long outdoor use. This type of vinyl chloride resin composition usually possesses high impact strength immediately after shaping, but once the shaped article is used outdoors, it can no longer maintain the high impact strength possessed immediately after shaping and such use abruptly reduces such strength. For this reason, use of this resin composition as a structural material has been extremely limited.

The principal cause for reduction in impact strength of the blended resin composition of vinyl chloride and MBS (or ABS) resins is due to numerous double bonds contained in butadiene. In other words, deterioration of the rubber component due to ultra-violet rays during outdoor use inevitably affects the properties of the MBS (or ABS) resin.

From this standpoint, such research and study has been performed to improve impact modifiers for the vinyl chloride resin by using a kind of rubber having excellent weather resistance other than butadiene rubber.

For example, US. Pat. No. 3,264,373 discloses a method, in which methylmethacrylate monomer is graft-polymerized upon a rubber copolymer of butadiene and alkyl acrylate, and British Pat. No. 1,027,710 discloses a method, in which vinyl chloride monomer is grafted upon a rubber copolymer of ethylene and vinyl acetate.

i resin or copolymers containing vinyl chloride as the principal constituent and from 5 to 30 parts by weight of a multi-component type resin obtained by salting-out These impact modifiers, however, are inferior in their ability to impart the impact strength to vinyl chloride resin as blended in comparison with the case of blending M88 or ABS resin with the vinyl chloride resin.

Some other impact modifiers give an extremely bad effect to vinyl chloride, when blended, in respect of kneadability and processabili'ty of the blended resin composition. Still some others cause considerable decrease in tensile strength of the resultant blend of vinyl chloride resin, and, moreover, another unfavorable phenomenon takes place such that when a sheet made of the blended vinyl chloride composition is bent or folded, there occurs whitening of the sheet at its bent portion.

The reason why both M88 and ABS resins have recently invited more attention from industries in general as the reinforcing agents for vinyl chloride resin is that they are not only excellent in their effect of imparting the impact strength to vinyl chloride resin, but also retain its various favorable properties such as processability, and so forth.

It is therefore an object of the present invention to provide a a vinyl chloride resin composition having excellent impact strength and weather resistance.

It is another object of the present invention to provide an improved method of producing an impact modifying component to be blended with vinyl chloride resin to give excellent impact strength and weather resistance to the resin composition.

The foregoing objects and other objects of the present invention will become more apparent from the following description of the invention and a few preferred examples thereof.

As the result of long and continuous studies made by the present inventors with the abovementioned problems in mind, it has been discovered that the intended vinyl chloride resin composition can be obtained by blending from 95 to parts by weight of vinyl chloride or acid deposition of a graft polymer latex produced from graftpolymerization of a monomer mixture consisting of styrene and methylmethacrylate, and containing a small quantity of cross-linking agent, upon a cross-linked copolymer rubber latex resulting from emulsion-polymerization of a monomer mixture consisting of butadiene and acrylic acid alkyl ester having the alkyl group of 2 to 12 carbon atoms and a small quantity of a cross-linking agent, or a monomer mixture consisting of acrylic acid alkyl ester, butadiene, methylmethacrylate, and a small quantity of a crosslinking agent and further graft-polymerization upon the resultant graft-polymer of methylmethacrylate containing therein a small quantity of cross-linking agent.

The invention will now be described in more detail hereinbelow.

A monomer mixture consisting of 60 to percent by weight of acrylic acid alkyl ester having an alkyl group of from 2 to 12 carbon atoms and 40 to 5 percent by weight of butadiene, or a monomer mixture consistting of 40 to 95 percent by weight of acrylic acid alkyl ester having an alkyl group of from 2 to 12 carbon atoms, 40 to 5 percent by weight of butadiene, and 0.1 to 30 percent by weight of methylmethacrylate is subjected to emulsion-polymerization in the presence of 0.01 to 3 percent by weight of a cross-linking agent to obtain a cross-linked copolymer rubber latex. More than 95 percent by weight of the rubber component in this latex has the particle size range of from 0.05 to 0.1 micron.

To the thus produced rubber latex containing therein 50 to 75 parts by weight of copolymer rubber, 50 to 25 parts by weight of a monomer mixture consisting of styrene and methylmethacrylate and containing therein 0.01 to 3 percent by weight of a cross-linking agent is added, and the batch is subjected to graft polymerization.

The emulsifier to be used in this emulsion polymerization is a higher fatty acid salt such as, for example, sodium stearate, potassium oleate, etc..

The free radical catalyst to be used for this emulsion polymerization, is for example cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, tertiary butyl hydroperoxide, alkali metals persulfate, ammonium persulfate. Further, in combination with such peroxide compounds, there may be used various reducing agent such as metals like iron, cobalt, etc., and a dialkali metal persulfate, etc. (as Redox catalyst).

The temperature for the emulsion polymerization usually ranges from to 80C in both rubber and graft polymerizations. The more preferable range is from 40 to 70C.

For the graft polymerization, there is a method, in which the components to be grafted upon the rubber latex are polymerized in a single stage. It has, however, been recognized that, when the graft polymerization is carried out in two stages, miscibility of the resulting multi-component type resin with vinyl chloride resin can be effectively improved. This is explained in more detail as follows.

The monomer component to be graft-polymerized upon therubber latex is divided into two portions of (l) to 90 percent by weight of monomer mixture consisting of styrene and methylmethacrylate with the former as the principal constituent and containing therein a small amount of a cross-linking agent; and (2) 90 to 10 percent by weight of methylmethacrylate containing therein a small quantity of a cross-linking agent. The first grafting component is first grafted upon the copolymer rubber latex, and, upon substantial completion of this first polymerization stage, the second grafting component is grafted.

A vinyl chloride resin composition, in which an impact modifier obtained by simply graft-polymerizing a monomer mixture consisting of styrene. methylmethacrylate, and/or acrylonitrile upon alkyl acrylate rubber latex is blended with vinyl chloride, has been well known. This graft polymer as an impact modifier, however, is poor in its miscibility with vinyl chloride resin with the consequence that the weather resistance, processability, and impact strength of the blended resin composition are not very satisfactory.

It has been found out, therefore, that the multicomponent type resin obtained by using the crosslinked copolymer rubber latex and by mixing a crosslinking agent into the monomer mixture of styrene and methylmethacrylate to be grafted upon this crosslinked copolymer rubber latex, according to the present invention, when used as the impact modifier, definitely imparts to vinyl chloride resin to be blended therewith an impact strength which is equal to or higher than that of the M85 resin, and, at the same time, yields the vinyl chloride resin composition having excellent weatherresistance, processability, tensile strength, and low stress-Whitening on bending.

In the present invention, the cross-linked copolymer obtained by emulsion polymerization of a monomer mixture consisting of acrylic acid alkyl ester and butadiene, or the monomer mixture, a part of which has been substituted for methylmethacrylate, should be essentially used as the trunk polymer.

The amount of butadiene to be copolymerized with acrylic acid alkyl ester, or a mixture monomer of acrylic acid alkyl ester and methylmethacrylate can be less than 40 percent by weight to give sufficient impactstrength-imparting-effect. When the amount exceeds 40 percent by weight, a problem arises with respect to the weather-resistance of the vinyl chloride resin com position, which cannot be solved without addition of a large quantity of expensive photo-stabilizer and antioxidation agent. This weather-resistance has been found to improve further by substituting a part of acrylic acid alkyl ester or butadiene constituting the monomer mixture for methylmethacrylate, which is then polymerized into a cross-linked terpolymer rubber. The quantity of methylmethacrylate to be substituted may preferably be from 0.1 to 30 percent by weight. A quantity exceeding 30 percent by weight would reduce the impactstrength-imparting effect to vinyl chloride resin.

As the acrylic acid alkyl ester to be used in the monomer mixture are those having the alkyl group of 2 to 12 carbon atoms such as, for example, ethyl acrylate, butyl acrylate, acryl acrylate, 2-methylbutyl acrylate, 2- ethyl-hexyl acrylate, and so forth.

The quantity of styrene and methylmethacrylate to be grafted on the cross-linked copolymer rubber should preferably be in the range of from 50 to 25 parts by weight with respect to from 50 to parts by weight of the cross-linked copolymer rubber. When the quantity of the rubber component is below 50 parts by weight, the impact-strength-imparting-effect to vinyl chloride resin is small, while the quantity above 75 parts by weight is liable to cause agglomeration at the time of the salting-out or acid deposition of the rubber component or at the time of blending with vinyl chloride resin powder with the result that no sufficient impactstrength-imparting effect can also be obtained.

It is further possible that, prior to the graft polymerization of styrene and methylmethacrylate monomer mixture containing a cross-linking agent upon the cross-linked copolymer rubber latex percent by weight of the rubber particles falls within the particle size range of from 0.05 to 0.1 micron), the coagulation of the rubber latex be carried out to bring the average particle size of the coagulated rubber particles to a range of from 0.12 to 0.3 micron. In this case, the coagulated particle is represented in terms of a diameter of the coagulate formed by assembly of spherical polymer particles.

For the coagulating agent, mineral acids such as hydrochloric acid, sulfuric acid, etc., inorganic salts, organic acids, and organic acid anhydride which are generally used as the latex coagulant may be used.

The rubber latex subjected to the coagulation operation exhibits further imparting effect to vinyl chloride resin in comparison'with the rubber latex which has not been coagulated. Also, such coagulated rubber minimizes or suppresses variations in the impact strength of shaped product of the vinyl chloride resin composition caused by difference in the degree of dispersion of the modifer, within polyvinyl chloride resulting from mixing and kneading, whereby constant, high impact strength of the shaped articles can be secured.

The cross-linking agent to be used in both'rubber and grafting components should be selected from among those which are readily polymerizable withthe'monomers. Examples of such cross-linking agents are: aromatic polyfunctional vinyl compounds such as divinylbenzene, divinyltoluene, etc., and glycol dimethacrylate compounds such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate. triethylene glycol dimethacrylate, etc..

The vinyl chloride resin for blending purposes according to the present invention is either homopolymer of vinyl chloride, or copolymer containing more than 70 percent by weight of vinyl chloride.

In order to enable skilled persons in the art to reduce the present invention to practice, the following preferred examples are presented. It should, however, be noted that these examples are illustrative only, and that any modification may be made thereof within the extent of protection as set forth in the appended claims.

EXAMPLE 1 The following component materials were charged into a stainless steel autoclave provided with an agitator, and polymerization was conducted at a temperature of 45C for 16 hours to obtain the rubber latex.

Cross-Linked Trunk Polymer Rubber 2-ethyl-hexyl acrylate 35 wt. parts Butadiene 20 do. Methylmethacrylate do. Ethyleneglycol dimethacrylate 0.65 do. Diisopropylbenzene hydroperoxide 0.13 do. Ferrous sulfate (FeSO .7H O) 0002 do. Ethylenediamine tetra-acetic acid disodium salt 0003 do. 7 Sodium formaldehyde sulfoxylate 0.03 do. Potassium oleate 0.6 do. Distilled water 190 do.

To the total amount of the rubber latex thus obtained, 0.065 part by weight of sodium sulfosuccinate dioctyl ester was added to sufficienty stabilize the same, after which 50 parts by weight of 0.2 percent hydrochloric acid aqueous solution was gradually added to coagulate.

The average particle size of the rubber latex after the coagulation was recognized to have increased to 0.17 1

First Grafting Component Styrene v wt. parts Methylmethacrylate 5 do. Divinylbenzenc 0.2 do. Diisopropylbenzene hydroperoxide 0.025 do. Sodium formaldehyde sulfoxylute 0.01 do.

Subsequently, a second grafting component of the following composition was added to the thus obtained graft polymer latex, and further polymerization was conducted for 7 hours at 60C.

Second Grafting Component Methylmethacrylate 15 wt. parts Divinylbenzene 0.2 do.

Diisopropylbenzene hydroperoxide 0.01 do. Sodium formaldehyde sulfoxylate 0005 do.

The resulted latex was found to contain approximately 28 percent of graft-copolymer, which indicates that the graft-polymerization was complete.

To this latex, 0.5 part by weight of 2,6-ditertiarybutyl-paracresole and 0.5 part by weight of dilaurylthiopropionate as the anti-oxidation agents were added, and, through the processes of the acid-deposition, dehydration, and desiccation, a multi-component type resin in powder form was obtained.

Next, 12.5 parts by weight. of this resin was added to 87.5 parts by weight of vinyl chloride resin (PD. 700) together with 2 wt. parts of dibutyltin maleate, and the batch was kneaded for three minutes by kneading rolls, thesurface temperature of which was maintained at 160C. The condition of the resin on the roll surface was recognized to have been well unified, which indicates that its processability is excellent.

From this kneaded resin composition, a plate of 3 mm thick was manufactured by press-forming under a pressure of 150 kg/cm at 195C.

The Charpy impact strength (according to ASTM-D- 256) of this sample plate was kg.cm/cm which figure is the remarkable increase in comparison with 3 kg.cm/cm of vinyl chloride resin alone.

Furthermore, a sample press sheet of 1 mm thick produced in the same manner as that of the abovementioned sample plate was bent, and the degree of stress-whitening through bending was observed. Substantially no whitening could be recognized.

Also, 90 parts by weight of vinyl chloride resin (P.D.

1,000) and 10 parts by weight of the abovementioned multi-component resin powder containing 4 wt. parts of a lead-type stabilizer (on mixture of 50 wt. percent of tribasic lead sulfate; 25 wt percent of dibasic lead stearate; 12.5 wt. percent of lead stearate; and 12.5 wt. of calcium stearate) and 0.2 wt part of carbon black was roll-kneaded at a temperature of 190C, and the blended resin composition was press-formed into a sample sheet of 3 mm thick under a pressure of kg/cm This plate was then subjected to an exposure test under artificially accelerated weathering conditions by means of a weather meter. The Charpy impact strength of this sample plate before light irradiation was 155 kg.cm/cm and that after 400 hours light irradiation was 130 kgcm/cm", which figure indicates the remarkably excellent weather-resistance that the plate possesses.

EXAMPLE 2 Multi-component polymer composition was produced in the same manner as in Example 1 above with 10 the exception that composition of the cross-linked r er and uantit of the cross-linkin trunk polymer ubb q t y g EXAMPLE 3 agent to be added to the component to be grafted on the rubber latex were varied as shown in Table 1 below. Multi-component type resin was produced by the Table 1 Second Graft Trunk Polymer Rubber First Graft Component Component (part by weight) (part by weight) (part by weight) OA Bu MMA EDMA ST MMA EDMA MMA EDMA Present Invention (*1 do. B do. do. do. do. do. do. 0.1 do. 0.1 do. C 54 1O 1 do. do. do. 0.15 do. 0.15 do. D 45 15 5 do. do. do. do. do. do. do. E ,40 2O 5 do. do. do. do. do. do. do. F 35 2O 10 do. do. do. do. do. do. do. G 35 2O 10 do. do. do. 0.30 do. 030 Reference Sample H 55 O 10 do. do. do. 0.15 do. 0.15 do. 1 0 5O 15 do. do. do. do. do. do. do. J 15 50 0 do. do. do. do. do do. do. K 50 10 5 do. do. do. 0 do. 0

NOTE OA: 2-ethyl-hexyl-acry1ate ST: styrene Bu: butadiene EDMA: ethylene glycol dimethacrylate MMA: methylmethacrylate DVB (divinyl benzene) These multi-component type resins were blended with vinyl chloride resin at a blending quantity of 12.5 wt. parts of the modifier resin and 87.5 wt. parts of vinyl chloride resin, and the properties of such resin compositions were tested. The results are as shown in 45 Table 2 below.

same manner as in Example 1 above with the exception that the coagulation of the rubber latex to be carried out prior to graft-polymerization of the first grafting component upon the rubber latex was not done, and that the composition of the trunk polymer rubber was varied as shown in Table 3 below.

Table 2 Charpy Impact Strength (k gem/cm Stress- Process- Exposure time Whitening ability (hours) Through 0 200 400 Bending Present Invention A 156 I25 75 54 1 do. B 160 107 77 Indicated do. C 135 84 75 Scarcely good graftwhitened ing even by do. D 154 132 125 I20 rollkneading do. E 163 139 130 105 do. F 137 133 130 I do. G 148 127 137 115 Reference Sample H 32 25 18 7 do. do. do. I 158 35 26 10 I do. do. do. .1 159 28 15 7 do. do. do. K 105 35 l7 l5 Notoriously Indicated whitened poor grafting by rollkneading Table 3 Trunk Polymer Rubber (part by weight) First Graft Component (part by weight) OA Bu MMA EDMA ST MMA EDMA MMA EDMA Present Invention L 5O 15 0.65 l l0 0.]5 0.15 do. M 45 5 do. do. do. do. do. do. do. N 40 2O 5 do. do. do. do. do. do. do. 0 35 10 do. do. do. do. do. do. Reference Sample P 50 0 10 do. do. do. do. do. do. do. 0 0 55 10 do. do. do. do. do. do. do. R 15 50 0 do. do. do. do. do. do. do. 5 55 10 0 0 15 20 0 0 0 do. T 55 l0 0 0 O 35 0 O 0 Table 4 Charpy Impact Strength (kg.cm/cm Stress- Exposure Time Whitening Process (hours) Through ability 0 I00 200 400 Bending Present Invention L 101 85 50 33 1 f Indicated do. M 85 8O 58 39 Scarcely good graftdo. N 98 81 73 35 whitened ing even by roll-kneading do. 0 105 87 55 33 Reference Sample P 30 26 17 5 do. do. do. Q 103 45 20 7 do. do. do. R 110 33 10 do. do. do. S 60 43 28 8 Notoriously Indicated whitened poor grafting by rollkneading do. T 68 40 22 10 do. do.

As w1ll be apparent from the above Tables, when the second grafting components, said first grafting coagulation is not carried out, the impact strength prior component being composed of styrene and methylto the light irradiation slightly declines, but the impact methacrylate with styrene as the principal constitustrength and the weather resistance of the resin compoent and containing therein the CI'OSSIlflklflg agent, sition are not affected. 40 and said second grafting component being com- What we claim is:

l. A method for producing vinyl chloride resin composition having excellent impact strength, weather resistance, and processability which consists essentially of uniforming blending:

95 to 70 parts by weight of a vinyl chloride polymer selected from the group consisting of homopolymers of vinyl chloride, and copolymers of vinyl chloride containing therein more than 70percent by weight of vinyl chloride, and 5 parts by weight of a multi-component type resin which is produced by the following steps:

. preparing a latex of a rubber polymer by polymerizing a monomer mixture selected from the group consisting of a mixture of to 95percent by weight of acrylic acid alkyl ester, 5 to 40percent by weight of butadiene, and 0.1 to 30percent by weight of methylmethacrylate in the presence of from 0.01 to 3percent by weight of crosslinking agent, said polymer latex containing from 50 to 75 parts by weight of said rubber polymer;

b. adding to said latex from 50 to 25 parts by weight of styrene and methylmethacrylate in a ratio of 90 to IOpercent by weight of styrene, 10 to 90percent by weight of methylmethacrylate and 0.01 to 3percent by weight ofa crosslinking agent copolymerizable with said monomers;

c. dividing said monomer components into first and posed of methylmethacrylate alone and containing therein the crosslinking agent;

d. adding said first grafting component to said crosslinked copolymer rubber latex to be graftpolymerized thereupon;

e. further adding said second grafting component to said graft-polymerized copolymer latex to be further grafted thereupon and f. recovering the multi-component type resin from said graft-polymerized latex through the processes of salting out, dehydration and drying.

2. The method according to claim 1, in which said acrylic acid alkyl ester has the alkyl group containing therein 2 to 12 carbon atoms and is selected from the group consisting of ethyl acrylate, butyl acrylate, acyl acrylate, 2-methyl-butyl acrylate, and 2-ethyl-hexyl acrylate.

3. The method according to claim 1, in which said crosslinking agent is one selected from the group consisting of divinyl benzene, divinyl tolulene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate.

4. The method according to claim 1, wherein said crosslinked copolymer rubber is coagulated, prior to the graft polymerization, by adding thereto a coagulat-- ing agent to obtain coagulated rubber particles of from 0.12 to 0.3 micron in average. 

1. A METHOD FOR PRODUCING VINYL CHLORIDE RESIN COMPOSITION HAVING EXCELLENT IMPACT STRENGTH, WEATHER RESISTANCE, AND PROCESSABLITITY WHICH CONSISTS ESSENTIALLY OF UNIFORMING BLENDING: 95 TO 70 PARTS BY WEIGHT OF A VINYL CHLORIDE POLYMER SELECTED FROM THE GROUP CONSISTING OF HOMOPOLYMERS OF VINYL CHLORIDE, AND COPOLYMERS OF VINYL CHLORIDE CONTAINING THEREIN MORE THAN 70PERCENT BY WEIGHT OF VINYL CHLORIDE, AND 5 30 PARTS BY WEIGHT OF A MULTI-COMPONENT TYPE RESIN WHICH IS PRODUCED BY THE FOLLOWING STEP: A. PREPARING A LATEX OF A RUBBER POLYMER BY POLYMERIZING A MONOMER MIXTURE SELECTED FROM THE GROUP CONSISTING OF A MIXTURE OF 40 TO 95 PERCENT BY WEIGHT OF ACRYLIC ACID ALKYL ESTER, 5 TO 40PERCENT BY WEIGHT OF BUTADIENE, AND 0.1 TO 30PERCENT BY WEIGHT OF METHYLMETHACRYLATE IN THE PRESENCE OF FROM 0.01 TO 3PERCENT BY WEIGHT OF CROSSLINKING AGENT, SAID POLYMER LATEX CONTAINING FROM 50 TO 75 PARTS BY WEIGHT OF SAID RUBBER POLYMER; B. ADDING TO SAID LATEX FROM 50 TO 25 PARTS BY WEIGHT OF STYRENE AND METHYLMETHACRYLATE IN A RATIO OF 90 TO 10PERCENT BY WEIGHT OF STYRENE, 10 TO 90PERCENT BY WEIGHT OF METHYLMETHACRYLATE AND 0.01 TO 3PERCENT BY WEIGHT OF A CROSSLINKING AGENT COPOLYMERIZABLE WITH SAID MONOMERS; C. DIVIDING SAID MONOMER COMPONENTS INTO FIRST AND SECOND GRAFTING COMPONENTS, SAID FIRST GRAFTING COMPONENT BEING COMPOSED OF STYRENE AND METHYLMETHACRYLATE WITH STYRENE AS THE PRINCIPAL COCONSTOTUTENT AND CONTAINING THEREIN THE CROSSLINKING AGENT, AND SAID SECOND GRAFTING COMPONENT BEING COMPOSED OF METHYLMETHACRYLATE ALONE AND CONTAINING THEREIN THE CROSSLINKING AGENT; D. ADDING SAID FIRST GRAFTING COMPONENT TO SAID CROSSLINKED COPOLYMER RUBBER LATEX TO BE GRAFT-POLYMERIZED THEREUPON; E. FURTHER ADDING SAID SECOND GRAFTING COMPONENT TO SAID GRAFT-POLYMERIZED COPOLMER LATEX TO BE FURTHER GRAFTED THEREUPON ANC F. RECOVERING THE MULTI-COMPONENT TYPE RESIN FROM SAID GRAFT-POLYMERIZED LATEX THROUGH THE PROCESSES OF SALTING OUT, DEHYDRATION AND DRYING.
 2. The method according to claim 1, in which said acrylic acid alkyl ester has the alkyl group containing therein 2 to 12 carbon atoms and is selected from the group consisting of ethyl acrylate, butyl acrylate, acyl acrylate, 2-methyl-butyl acrylate, and 2-ethyl-hexyl acrylate.
 3. The method according to claim 1, in which said crosslinking agent is one selected from the group consisting of divinyl benzene, divinyl tolulene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate.
 4. The method according to claim 1, wherein said crosslinked copolymer rubber is coagulated, prior to the graft polymerization, by adding thereto a coagulating agent to obtain coagulated rubber particles of from 0.12 to 0.3 micron in average. 